JPH09179253A - Development processing method for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a negative image high enough in contrast by using a stable developing solution of a pH<11.0 and an always stable image small in fluctuation of photographic performance at the time of replenishing a small amount to the developing solution and restrained from occurrence of uneven development. SOLUTION: This silver halide photographic sensitive material contains a hydrazine nucleator specified in structure and a nucleation promotor in a photosensitive silver halide emulsion layer and/or another hydrophilic colloidal layer, and upon ending exposure processed with the developing solution having a replenishing solution fed in an amount of <=225ml/m<2> and comprising (1) a dihydroxybenzene type developing agent in 0.2-0.75mol/l, (2) a 1-phenyl-3- pyrazolidone or p-aminophenol type assistant developing agent in 0.001-0.06mol/l, (3) a free sulfite ion in 0.3-1.2mol/l, and (4) a mercaptothiazole derivative having a specified substituent having a pH of 9.0-11.0.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a development processing method using a silver halide black-and-white photographic light-sensitive material to form an ultrahigh contrast image at pH = 11.0 or less. The present invention relates to a development processing method in which

[0002]

2. Description of the Related Art In the field of graphic arts, in order to obtain good halftone dot images and characters and line images,
What is needed is a system for forming ultrahigh contrast photographic images in which image areas and non-image areas are clearly distinguished. The formation of ultrahigh contrast photographic images has been carried out for many years using a special developer called a lith developer. In the system using the lith developer, it is essential to keep the concentration of free sulfite ion in the developer extremely low in order to realize its performance. Since the sulfite ion functions as a preservative for the developing solution, the lith developer has a problem that it lacks stability and deteriorates significantly over time.

The addition of hydrazine compounds to silver halide photographic emulsions and developers is described in US Pat. No. 3,730,7.
No. 27 (Developer combining ascorbic acid and hydrazine), No. 3,227,552 (using hydrazine as an auxiliary developing agent for directly obtaining a color positive image), No. 3,386,831 (silver halide) Contains β-mono-phenylhydrazine, an aliphatic carboxylic acid, as a stabilizer for sensitive materials), No. 2,419,975, and by Mees.
The Theory of Photographic Process (T
he Theory of Photographic Prosess) 3rd Edition (1966)
Year) 281 pages, etc.

Among these, in particular US Pat. No. 2,41.
No. 9,975 discloses that a hard negative image can be obtained by adding a hydrazine compound. The patent specification adds a hydrazine compound to a silver chlorobromide emulsion,
When developed with a developer having a high pH such as 12.8,
It is described that extremely hard photographic characteristics having a gamma (γ) of more than 10 can be obtained. However, a strong alkaline developer having a pH close to 13 is liable to be oxidized by air and is unstable, and cannot withstand long-term storage or use.

Attempts have been made to develop a high-contrast image by developing a silver halide light-sensitive material containing a hydrazine compound with a developer having a lower pH. JP-A-1-17993
No. 9 and JP-A-1-179940, a photosensitive material containing a nucleation development accelerator having an adsorbing group for silver halide emulsion grains and a nucleating agent also having an adsorbing group was used to obtain a pH of 11.0. The processing method of developing with the following developing solution is described. However, when a compound having an adsorptive group is added to a silver halide emulsion, if it exceeds a certain limit, the photosensitivity may be impaired, the development may be suppressed, or the action of other useful adsorptive additives may be hindered. Therefore, the amount used is limited, and sufficient hardness cannot be achieved. JP-A-60-140343 discloses that the addition of amines to a silver halide photographic light-sensitive material improves the contrast. However, at pH 11.
In the case of developing with a developing solution of less than 0, sufficient contrast cannot be expressed. JP-A-56-106244 discloses that
By adding an amino compound to a developer having a pH of 10 to 12,
It is disclosed to promote contrast. However, when amines are used by adding them to a developing solution, there are problems such as odor of the solution and stains due to adhesion to equipment used, or environmental pollution due to waste solution, and it is desired to incorporate it into a light-sensitive material. It has not yet been found that it can be added to a light-sensitive material to obtain sufficient performance.

US Pat. Nos. 4,998,604 and 49,
No. 94365 discloses a hydrazine compound having a repeating unit of ethylene oxide and a hydrazine compound having a pyridinium group. However,
As is clear from these examples, the contrast is not sufficient, and it is difficult to obtain the contrast and the required Dmax under practical development processing conditions.

In order to obtain a super-high contrast image by using a stable developing solution having a pH of less than 11.0, various investigations have been conducted, and a specific hydrazine nucleating agent and a specific quaternary onium salt nucleation promoting agent are contained in a light-sensitive material. It has been found that a super-high contrast image can be obtained by using the agent together. However, even in this method, the replenishing amount of the developing solution is required to be about 320 to 450 ml when processing 1 square meter of the silver halide photographic light-sensitive material, and a further replenishing amount reducing method and a stable processing method are desired. When the replenishment amount is reduced, there is a problem that silver sludge in the developing tank increases and adheres to the photosensitive material.

It is known to reduce the change in photographic performance by reducing the change in pH value of the developer,
Stabilizing photographic performance by increasing the buffering capacity of a developing solution is disclosed in Japanese Patent Publication No. 3730/1993. However, when a silver halide photographic light-sensitive material is processed with an automatic processor using a developer having an increased buffering capacity, it has a drawback that uneven development is likely to occur.

It is known to supply a developing solution as a solid processing agent, and JP-A-61-259921 describes that the stability of the developing solution as a solid processing agent is enhanced. Further, JP-A-5-265147 discloses a processing method in which a developing solution for processing a hydrazine-containing photosensitive material is supplied as a solid processing agent, and it is disclosed that black spots are improved.

[0010]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to obtain a sufficiently hard negative image with a stable developing solution having a pH of less than 11.0 and to improve the photographic performance with a small replenishing amount of the developing solution. Variation is small, and development unevenness is small,
It is an object of the present invention to provide a development processing method for a silver halide black-and-white photographic light-sensitive material that can always obtain stable performance.

[0011]

The object of the present invention is to have at least one light-sensitive silver halide emulsion layer on a support, and in the emulsion layer or other hydrophilic colloid layer, a hydrazine group near At least one selected from a hydrazine-based nucleating agent or a compound represented by the following general formula (I), characterized by having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine After exposing a silver halide photographic light-sensitive material characterized by containing a hydrazine nucleating agent and a nucleation accelerator, (1).
2 to 0.75 mol / liter of dihydroxybenzene type developing agent, (2) 0.001 to 0.06 mol / liter of 1-phenyl-3-pyrazolidone type or p-aminophenol type auxiliary developing agent, (3) It contains 0.3 to 1.2 mol / liter of free sulfite ion, (4) a compound represented by the following general formula (II), and has a pH of 9.0 to 1.
With a developing solution of 1.0, the replenishing amount of the developing solution is 225 ml /
It was achieved by a method of developing and processing a silver halide photographic light-sensitive material characterized by processing at m ² or less. General formula (I)

[0012]

[Chemical 6]

In the formula, R ₀ represents a difluoromethyl group or a monofluoromethyl group, and A ₀ represents an aromatic group.
However, A ₀ is at least one diffusion resistant group, an adsorption promoting group on silver halide, an alkylthio group, an arylthio group,
Heterocyclic thio group, quaternary ammonium group, nitrogen-containing heterocyclic group containing quaternized nitrogen atom, alkoxy group containing ethyleneoxy or propyleneoxy unit, or saturated heterocyclic group containing sulfide bond or disulfide bond, or these Having the combination of as a substituent. General formula (II)

[0014]

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In the formula, Y and Z are N or CR ₂ (R ₂ represents an alkyl group or an aryl group), R ₁ is -SO ₃ M,-
_{COOM, -OH, -NHSO 2 R 3} , -SO 2 NR 3
An alkyl group, an aryl group or a heterocyclic group or an alkyl group, an aryl group or a heterocyclic group substituted with at least one member selected from the group consisting of R ₄ and —NR ₅ CONR ₃ R ₄ are formed via a linking group. Represents a group represented by
R ₃ , R ₄ and R ₅ represent a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms. M is a hydrogen atom, an alkali metal atom,
Represents quaternary ammonium and quaternary phosphonium.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The hydrazine-based nucleating agent used in the present invention will be described. The hydrazine nucleating agent used in the present invention has an anionic group in the vicinity of a hydrazine group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine, and a general formula (I ) Is a hydrazine derivative represented by. First, the former will be described in detail.

Specific examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid and salts thereof. Here, the vicinity of the hydrazine group means an atom selected from at least one of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom between a nitrogen atom and an anionic group near the anionic group of hydrazine.
It means that a binding chain formed by the individual is interposed. More preferably, a bond chain formed by 2 to 5 atoms selected from at least one of a carbon atom and a nitrogen atom is present as the vicinity, and a bond chain formed by 2 to 3 carbon atoms is more preferable. It is the case of intervening. The nonionic group that forms an intramolecular hydrogen bond with hydrazine hydrogen is a group in which a lone electron pair forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring, and has at least an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom. A group having one. Examples of the nonionic group include an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group, an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group, and an acylamino group. Of these, anionic groups are preferred, and carboxylic acids and salts thereof are most preferred. Preferred nucleating agents used in the present invention are those represented by the following formulas (A), (B) and (C). General formula (A)

[0018]

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(Wherein R ¹ represents an alkyl group, an aryl group or a heterocyclic group, L ¹ represents a divalent linking group having an electron-withdrawing group, Y ¹ represents an anionic group or a hydrogen atom of hydrazine). Represents a nonionic group forming an intramolecular hydrogen bond.) General formula (B)

[0020]

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(Wherein R ² represents an alkyl group, an aryl group or a heterocyclic group, L ² represents a divalent linking group, and Y
² represents an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine. ) General formula (C)

[0022]

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(In the formula, X ³ represents a group capable of substituting on a benzene ring, R ³ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group or an amino group, and Y ³ represents An anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine, m ³ is an integer of 0 to 4, n ³ is 1 or 2. When n ³ is 1, R ³ is It has an electron-withdrawing group.)

The general formulas (A), (B) and (C) will be described in more detail. The alkyl group of R ¹ and R ² is a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, t-butyl, Allyl, propargyl, 2-butenyl, 2-hydroxyethyl, benzyl, benzhydryl, trityl, 4-methylbenzyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms, for example, phenyl, naphthyl, p-alkoxyphenyl, p-sulfonamidophenyl, p-ureidophenyl, p-amidophenyl. Is. The heterocyclic group is a 5-membered or 6-membered saturated or unsaturated heterocycle containing at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. The type of the element may be one or plural, and examples thereof include 2-furyl, 2-thienyl, and 4-pyridyl.

An aryl group is preferred as R ¹ and R ² .
An aromatic heterocyclic group or an aryl-substituted methyl group,
More preferably, it is an aryl group (eg phenyl, naphthyl). R ¹ and R ² may be substituted with a substituent, and examples of the substituent include an alkyl group, an aralkyl group,
An alkoxy group, an alkyl- or aryl-substituted amino group,
Amide group, sulfonamide group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group,
A sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, and a phosphoric acid amide group. These groups may be further substituted. Of these, a sulfonamide group, a ureido group, an amide group, an alkoxy group, and a urethane group are preferable, and a sulfonamide group and a ureido group are more preferable. When possible, these groups may be linked to each other to form a ring.

The alkyl group of R ^3, aryl group, heterocyclic group include those described in R ^1. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, such as vinyl and 2-styryl. The alkynyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and examples thereof include ethynyl and phenylethynyl. The alkoxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms.
Linear, branched or cyclic alkoxy group such as methoxy, isopropoxy and benzyloxy.
The amino group has 0 to 16 carbon atoms, preferably 1 carbon atom.
-10, and are ethylamino, benzylamino and phenylamino. When n ³ = 1, R ³ is preferably an alkyl group, an alkenyl group, or an alkynyl group. n ³ =
In the case of 2, R ³ is preferably an amino group or an alkoxy group.

The electron-withdrawing group contained in R ³ has a Hammett σ _m value of 0.2 or more, preferably 0.3.
As described above, for example, a halogen atom (fluorine, chlorine, bromine), a cyano group, a sulfonyl group (methanesulfonyl, benzenesulfonyl), a sulfinyl group (methanesulfinyl), an acyl group (acetyl, benzoyl), an oxycarbonyl group (methoxycarbonyl) ), Carbamoyl group (N-methylcarbamoyl), sulfamoyl group (methylsulfamoyl), halogen-substituted alkyl group (trifluoromethyl), heterocyclic group (2-benzoxazolyl, pyrrolo), quaternary onium group (tri Phenylphosphonium, trialkylammonium, pyridinium). Examples of R ³ having an electron-withdrawing group include trifluoromethyl, difluoromethyl, pentafluoroethyl, cyanomethyl, methanesulfonylmethyl, acetylethyl, trifluoromethylethynyl and ethoxycarbonylmethyl.

L ¹ and L ² represent a divalent linking group, and include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent heterocyclic group, and -O-, -S-,
It is a group in which groups such as —NH—, —CO—, and —SO ₂ — are used alone or in combination. L ¹ and L ² are R
^It may be substituted with the group described as the substituent of ¹ . Examples of the alkylene group include methylene, ethylene, trimethylene, propylene, 2-butene-1,4-yl, 2
-Butyn-1,4-yl. The alkenylene group is, for example, vinylene. The alkynylene group is ethynylene. The arylene group is, for example, phenylene. The divalent heterocyclic group is, for example, furan-1,4-diyl. L ¹ is an alkylene group,
An alkenylene group, an alkynylene group and an arylene group are preferable, and an alkylene group is more preferable. Further, an alkylene group having a chain length of 2 to 3 carbon atoms is most preferable. L ² is an alkylene group, an arylene group, —NH-alkylene-,
-O-alkylene- and -NH-arylene- are preferable, and -NH-alkylene- and -O-alkylene- are more preferable.

The electron-withdrawing group of L ¹ includes R ³
Examples of the electron-withdrawing group of the above include.
Examples of L ¹ include tetrafluoroethylene, fluoromethylene, hexafluorotrimethylene, perfluorophenylene, difluorovinylene, cyanomethylene, and methanesulfonylethylene.

Y ¹ to Y ^{3 are} as described above, and are anionic groups or nonionic groups in which a lone electron pair forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring. More specifically, examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid, and salts thereof. Examples of the salt include alkali metal ions (sodium and potassium), alkaline earth metal ions (calcium and magnesium), ammonium (ammonium, triethylammonium, tetrabutylammonium, pyridinium) and phosphonium (tetraphenylphosphonium). As the nonionic group, an oxygen atom, a nitrogen atom, a group having at least one of a sulfur atom and a phosphorus atom, an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group,
Examples thereof include an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group and an acylamino group. Y ¹ to Y ³ are preferably anionic groups, and more preferably carboxylic acids and salts thereof.

Examples of the group capable of substituting on the benzene ring of X ³ and its preferable group include those mentioned as the substituents contained in R ¹ of the general formula (A). When m ³ is 2 or more, they may be the same or different.

R ¹ to R ³ or X ³ may have a diffusion resistant group used in a photographic coupler or may have an adsorption promoting group to silver halide. The diffusion-resistant group has 8 to 30 carbon atoms, and preferably has 12 to 25 carbon atoms. As the adsorption-promoting group for silver halide, thioamides (eg, thiourethane,
Thioureido, thioamide), mercaptos (eg 5
-Mercaptotetrazole, 3-mercapto-1,2,2
Heterocyclic mercapto such as 4-triazole, 2-mercapto-1,3,4-thiadiazole, and 2-mercapto-1,3,4-oxadiazole, alkylmercapto,
Aryl mercapto) and a 5- or 6-membered nitrogen-containing heterocycle (eg benzotriazole) which produces silver imino
It is. Examples of those having a silver halide adsorption promoting group include those having a structure in which the adsorptive group is protected and the protective group is removed at the time of development to increase the adsorptivity to silver halide.

In the general formulas (A), (B) and (C),
The radicals from which the hydrogen atoms of the two compounds are removed may combine with each other to form a bis type. In the general formulas (A), (B), and (C), the general formulas (A) and (B) are preferable, and the general formula (A) is more preferable. Further, in the general formulas (A), (B) and (C), the following general formulas (D), (E) and (F) are more preferable, and the general formula (D) is most preferable. General formula (D)

[0035]

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(In the formula, R ⁴ , X ⁴ and m ⁴ have the same meanings as R ³ , X ³ and m ^{3 in} formula (C), respectively, and L ⁴ , Y ^{4 and}
Is synonymous with L ¹ and Y ¹ of the general formula (A). ) General formula (E)

[0037]

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(In the formula, R ⁵ , X ⁵ and m ⁵ are respectively synonymous with R ³ , X ³ and m ^{3 of the} general formula (C), and L ⁵ , Y ^{5 and}
Is synonymous with L ² and Y ^{2 in} the general formula (B). ) General formula (F)

[0039]

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(In the formula, R⁶¹, R⁶², X⁶, M⁶, N⁶,
Y is R in the general formula (C)^Three, R^Three, X ^Three, M^Three, N^Three, Y
^ThreeIs synonymous with )

Specific examples of the nucleating agent used in the present invention are shown below, but the present invention is not limited thereto.

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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Next, the hydrazine derivative represented by the general formula (1) will be described in detail. General formula (1)

[0049]

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In the formula, R ₀ represents a difluoromethyl group or a monofluoromethyl group, and A ₀ represents an aromatic group.
However, at least one of the substituents possessed by A ₀ is a diffusion resistant group, a silver halide adsorption promoting group, an alkylthio group, an arylthio group, a heterocyclic thio group, a quaternary ammonium group,
A nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, an alkoxy group containing an ethyleneoxy or propyleneoxy unit, or a saturated heterocyclic group containing a sulfide bond or a disulfide bond, or at least one of these groups It is a substituent containing.

Among the compounds represented by the general formula (1), preferable compounds are represented by the following general formula (1-a). General formula (1-a)

[0052]

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In the formula, R1 represents a difluoromethyl group or a monofluoromethyl group, A1 represents a divalent aromatic group, R2 and R3 represent a divalent aliphatic group or aromatic group, and L1 and L2 are It represents a divalent linking group, and m2 and m3 each independently represent 0 or 1. X1 is a diffusion-resistant group, a group promoting adsorption to silver halide, an alkylthio group, an arylthio group, a heterocyclic thio group, a quaternary ammonium group, a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom,
It represents an alkoxy group containing an ethyleneoxy or propyleneoxy unit, or a saturated heterocyclic group containing a sulfide bond or a disulfide bond.

Among the compounds represented by the general formula (1-a), preferred compounds are represented by the following general formula (1-b). General formula (1-b)

[0055]

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In the formula, X11, R11, R21, R31, L21, m21
And m31 represent X in the general formula (1-a), respectively.
1, R1, R2, R3, L2, m2 and m3 are the same as defined above, Y represents a substituent, and n represents an integer of 0 to 4. Next, the compound represented by formula (1) will be described in detail. In the general formula (1), the aromatic group represented by A ₀ is a monocyclic or bicyclic aryl group and an aromatic heterocyclic group. Specific examples include a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, an isoquinoline ring, a pyrrole ring, a furan ring, a thiophene ring, a thiazole ring and an indole ring. A ₀ preferably contains a benzene ring, and particularly preferably a benzene ring. A ₀ may be substituted with a substituent. Examples of the substituent include an alkyl group, an aralkyl group, an aryl group,
Alkoxy, aryloxy, hydroxy, acyloxy, acyl, oxycarbonyl, carbamoyl, N-sulfonylcarbamoyl, carboxyl, substituted amino, acylamino, sulfonamide, ureido, urethane, sulfonyl Ureido group,
Alkylthio, arylthio, sulfonyl, sulfamoyl, acylsulfamoyl, carbamoylsulfamoyl, sulfo, cyano, halogen, phosphinyloxy, phosphinylamino, sulfamoylamino And an oxamoylamino group. These groups may be further substituted. Among these, a sulfonamide group, a ureido group, an acylamino group, a carbamoyl group, an alkoxy group, a substituted amino group, an alkyl group, and an oxycarbonyl group are preferred, and a sulfonamide group and a ureido group are particularly preferred. Next, the specific group which the substituent of A ₀ should have is described in detail.
The diffusion resistant group means a diffusion resistant group in a photographic coupler or the like, a so-called ballast group, which is used when the compound of the present invention is added to a specific silver halide emulsion layer. Is a group that can easily prevent diffusion to other layers, or a group that can be prevented from being easily eluted in a developing solution during development. Specifically, it is a group having 8 or more total carbon atoms, preferably 8 to 16 total carbon atoms. As the ballast group, preferably, an alkyl group, an aryl group, an alkoxy group, an aryl group having 8 or more total carbon atoms is used. Examples include an oxy group, an oxycarbonyl group, a carbamoyl group, an acylamino group, a sulfonamide group, a carbonyloxy group, a ureido group, a sulfamoyl group, and a combination thereof. When A ₀ has a ballast group, the total number of carbon atoms of A ₀ including the ballast group is 14 or more.

The adsorption promoting group to silver halide is preferably a thioamide group, a mercapto group, a group having a disulfide bond or a 5- or 6-membered nitrogen-containing heterocyclic group. The thioamide adsorption promoting group is a divalent group represented by -CS-amino- and may be a part of the ring structure or may be an acyclic thioamide group.
Useful thioamide adsorption promoting groups are described, for example, in US Pat.
30,925, 4,031,127, 4,08
Nos. 0,207, 4,245,037, 4,25
Nos. 5,511, 4,266,013 and 4,2
76, 364, and "Research Disclosure," Vol. 151, No. 1.
5162 (November 1976), and Vol. 176, N
o. 17626 (December 1978).

Specific examples of the acyclic thioamide group are, for example, thioureido group, thiourethane group, dithiocarbamic acid ester group and the like, and specific examples of the cyclic thioamide group are, for example, 4-thiazoline-2-thione, 4- Imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-triazoline-3-thione, 1,3.
4-thiadiazoline-2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, and the like. It may be substituted. As the mercapto group, an aliphatic mercapto group, an aromatic mercapto group or a heterocyclic mercapto group (when the carbon atom to which the —SH group is bonded is a nitrogen atom next to it, a cyclic thioamide group having a tautomer relationship with Are synonymous, and specific examples of this group are the same as those listed above).

Examples of the 5- to 6-membered nitrogen-containing heterocyclic group include 5- to 6-membered nitrogen-containing heterocycles consisting of a combination of nitrogen, oxygen, sulfur and carbon. Among these, preferred are benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, triazine and the like.
These may be further substituted with a suitable substituent.
Preferred as the adsorption promoting group is a cyclic thioamide group (that is, a mercapto-substituted nitrogen-containing heterocycle, for example, 2
-Mercaptothiadiazole group, 3-mercapto-1,
2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4-oxadiazole group, 2-mercaptobenzoxazole group, etc.), or a nitrogen-containing heterocyclic group forming iminosilver (for example, , A benzotriazole group, a benzimidazole group, an indazole group, etc.). In the present invention, the adsorption promoting group includes its precursor. The precursor is an adsorption promoting group with a precursor group, which is released by the developing solution for the first time during development, and reacts with hydroxide ion or sulfite ion in the developing solution or with a developing agent. It is disassembled as a scratch. Specifically, a carbamoyl group, a 1,3,3a, 7-tetrazainden-4-yl group, a uracil group, an alkoxycarbonyl group, or the 4-position is substituted with an ureido group, a sulfonamide group, or an amide group. 4-substituted-2,5-dihydroxyphenyl group and the like can be mentioned.

The alkylthio group is a substituted or unsubstituted, branched, cyclic or linear chain having 1 to 18 carbon atoms.
The alkylthio group of is preferably a substituent thereof,
An aryl group, an alkoxy group (including an alkoxy group containing repeating ethyleneoxy or propyleneoxy units), a carboxyl group, a carbonyloxy group, an oxycarbonyl group, an acylamino group, a quaternary ammonium group,
Examples thereof include an alkylthio group, a heterocyclic group, a sulfonamide group, and a ureido group. Specific examples of the alkylthio group include the following groups.

[0061]

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The arylthio group is a substituted or unsubstituted arylthio group having a total of 6 to 18 carbon atoms, and as the substituent, the substituent which A ₀ of the general formula (1) may have has been described. The same thing as is mentioned. The arylthio group is preferably a substituted or unsubstituted phenylthio group, specifically, a phenylthio group and 4-τ.
-Butylphenylthio group, 4-dodecylphenylthio group and the like.

The heterocyclic thio group is a substituted or unsubstituted, saturated or unsaturated heterocyclic thio group having 1 to 18 carbon atoms, and contains one or more oxygen atom, nitrogen atom, or sulfur atom. It is a 5- or 6-membered monocyclic heterocycle or a condensed heterocycle. Specifically, a benzothiazolylthio group, a 1-phenyl-5-tetrazolylthio group, 2
-Mercaptothiadiazolyl-4-thio group, pyridyl-
2-thio group and the like can be mentioned.

The quaternary ammonium group represents a quaternary aliphatic ammonium cation or a quaternary aromatic ammonium cation, and their counter anions. It may be a cyclic quaternary ammonium group, and the total carbon number of the quaternary ammonium cation is preferably 3 to 24. As the counter anion, specifically, chloro anion, bromo anion,
Examples thereof include an iodine anion, a sulfonate anion, and a carboxylate anion. When the compound represented by the general formula (1) has a sulfo group, a carboxyl group, or the like, an inner salt may be formed.

When X represents a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, specific examples thereof include pyridinium group, quinolinium group, isoquinolinium group, phenanthrinium group, triazolinium group and imidazoli group. And a benzothiazolinium group. These groups may be further substituted with a substituent, but the substituent is preferably an alkyl group, an aryl group, an alkoxy group, an alkylcarbamoyl group, an amino group, an ammonium group or a heterocyclic group.

The alkoxy group containing an ethyleneoxy or propyleneoxy unit is specifically R ₄ -O- (CH ₂ CH ₂
O) _p- , R ₄ -O- ｛CH ₂ CH (CH ₃ ) O｝ _p- or R ₄ -O-
It is an alkoxy group represented by {CH ₂ CH (OH) CH ₂ O} _p − or the like. Here, p represents an integer of 1 or more, and R ₄
Represents an aliphatic group or an aromatic group. R ₄ is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. Specifically, CH ₃ O (CH ₂ CH ₂ O) ₃ −, C ₆ H ₁₃ O
(CH ₂ CH ₂ O) ₂ −, C ₄ H ₉ O− (CH ₂ CH ₂ CH ₂ O) ₂ −, C ₈ H ₁₇ OCH _{2
CH (OH) CH 2 O -} , C 12 H 25 O- {CH 2 CH (CH 3) O} 2 -, C 2 H
₅ O (CH ₂ CH ₂ O) _6- , and the like.

The saturated heterocyclic group containing a sulfide bond or a disulfide bond is specifically -S- or -S-.
It represents a 5- or 6-membered saturated heterocycle containing an S-bond and is preferably a group shown below.

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Next, the compound represented by formula (1-a) will be described. In the general formula (1-a), A ₁ represents a divalent aromatic group, which is the same as the general formula (1-a) except that the substituent that A ₀ should have is more limited. It is a group having almost the same meaning as A _{0 in} (1), and its preferable range is also the same. That is, the divalent aromatic group represented by A ₁ in the general formula (1-a) is preferably
It is a monocyclic arylene group, more preferably a phenylene group. When A ₁ represents a phenylene group, this may have a substituent. Examples of the substituent of the phenylene group include those described for the substituent of A _{0 in} the general formula (1), and preferably an alkyl group, an alkoxy group, a hydroxy group, an amino group, an alkylamino group, an acylamino group. , Sulfonamide group, ureido group,
It is a halogen atom, a carboxyl group, a sulfo group, etc., and the total number of carbon atoms in these groups is 1 to 12, particularly preferably 1
８8. When A ₁ represents a phenylene group, particularly preferably when A ₁ represents an unsubstituted phenylene group.

In the general formula (1-a), R2 and R3 are 2
Represents a valent aliphatic group or aromatic group. The divalent aliphatic group is a substituted or unsubstituted, linear, branched or cyclic alkylene group, alkenylene group or alkynylene group, and the aromatic group is a monocyclic or bicyclic arylene group. R2 and R3 are preferably an alkylene group or an arylene group, and most preferably R2 represents a phenylene group and R3 represents a phenylene group or an alkylene group. These are represented by A in the general formula (1).
_It may have the same substituent as described for the substituent of ₀ .

In the general formula (1-a), the divalent linking group represented by L1 and L2 means --O--, --S--, --N.
(R _N) - (R _N represents a hydrogen atom, an alkyl group or an aryl group,.), - CO -, - SO 2 -, group alone etc., or a group composed of a combination of these groups.
The group consisting of a combination here specifically means -CO.
_{N (R N) -, -} SO 2 N (R N) -, - COO -, -
_{N (R N) CON (R} N) -, - SO 2 N (R N) CO
_{-, - SO 2 N (R} N) CON (R N) -, - N
_{(R N) COCON (R N} ) -, - N (R N) SO 2 N
(R _N )-and the like. In the general formula (1-a), L
1 is preferably -SO ₂ NH -, - NHCONH-,
-O -, - S -, - N (R N) - a, and most preferably -SO ₂ NH -, - it is -NHCONH-. L2 is _{preferably, -CON (R N) -,} - SO 2 NH -, - N
_{HCONH -, - N (R N} ) CONH -, - is COO-. Here L ₂ is -CON (R _N) - or -N
When representing the (R _N) CONH-, as R _N is a substituted alkyl group, it may be a represent the -R ₃ -X groups in Formula (1-a).

In the general formula (1-a), X1 is a diffusion resistant group, an adsorption promoting group on silver halide, an alkylthio group,
It represents an arylthio group, a heterocyclic thio group, a quaternary ammonium group, a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, an alkoxy group containing an ethyleneoxy or propyleneoxy unit, or a heterocyclic group containing a disulfide bond. These are the same as those described above as the substituent of A ₀ in the general formula (1) or the group contained in the substituent. In the general formula (1-a), X1 is an alkylthio group,
When representing an arylthio group, a heterocyclic thio group, a quaternary ammonium group, an alkoxy group containing an ethyleneoxy or propyleneoxy unit, or a heterocyclic group containing a disulfide bond, R3 is preferably an alkylene group,
m3 represents 1. When X1 in the formula (1-a) represents a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, the nitrogen-containing heterocyclic group is quaternized by the bond between the nitrogen atom and R3. In some cases, the nitrogen-containing heterocyclic group originally quaternized binds to L2 or L1 without via R3. In the former, m3 is 1 and R3 is preferably an alkylene group; in the latter, m3 represents 0.

Among the compounds represented by the general formula (1-a), more preferable compounds are represented by the general formula (1-b). Wherein X11, R11, R21, R31, L21, m21 and m
31 represents X 1, R 1, and R 1 in the general formula (1-a), respectively.
R2, R3, L2, m2 and m3 are the same as defined above,
Y represents a substituent, and n represents an integer of 0 to 4. The substituent represented by Y has the same meaning as that described for the substituent that A1 may have in formula (1-a), and the preferred range is also the same. n is preferably 0 or 1, and more preferably n is 0.

In the compound represented by the general formula (1-b), when X11 represents an alkylthio group, more preferable ones are those represented by the following general formula (1-c). General formula (1-c)

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In the formula, R ₁₂ is the same as R ₁₁ in the general formula (3), and R ₅ represents an alkylene group. L ₃₂ is
In connection with a benzene ring, it represents an acylamino group, a carbamoyl group, a ureido group, an oxycarbonyl group or a sulfonamide group. When L ₃₂ represents an acylamino group, an oxycarbonyl group or a sulfonamide group, m ₄ represents 1, and when L ₃₂ represents a carbamoyl group or an ureido group, m ₄ represents 1 or 2. When m ₄ is 1, R ₆
Is an unsubstituted alkyl group having a total carbon number of 7 or more, a total carbon number of 1 to
18 represents a substituted alkyl group or a cycloalkyl group having 3 or more carbon atoms in total, and when m ₄ is 2, R ₆ is 1 to 1 carbon atoms in total.
8 represents a substituted or unsubstituted alkyl group or a cycloalkyl group having a total carbon number of 3 or more.

The compounds of the present invention are exemplified below, but the present invention is not limited thereto.

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[0079]

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[0081]

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[0082]

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[0083]

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[0084]

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The hydrazine nucleating agent of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, It can be used by dissolving it in methyl cellosolve or the like. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, a powder of a hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or an ultrasonic wave by a method known as a solid dispersion method and used.

The hydrazine nucleating agent of the present invention may be added to any of the silver halide emulsion layer on the silver halide emulsion layer side of the support or any other hydrophilic colloid layer. It is preferably added to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the nucleating agent of the present invention is 1 × 10 ⁻⁶ to 1 × with ^respect to 1 mol of silver halide.
10 ⁻² mol is preferred, 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol is more preferred, and 2 × 10 ^{−5 to} 5 × 10 ⁻³ mol is most preferred.

The nucleation accelerator used in the present invention includes
Examples thereof include amine derivatives, onium salts, disulfide derivatives and hydroxymethyl derivatives. Examples are listed below. JP-A-7-77783, pages 49 to 5
Compounds A-1) to A-73) described on page 8. JP-A-7-
Compounds represented by (Chemical Formula 21), (Chemical Formula 22) and (Chemical Formula 23) described in No. 84331, specifically, the compounds described on pages 6 to 8 of the same publication. Compounds represented by the general formula [Na] and the general formula [Nb] described in JP-A-7-104426, specifically Na described on pages 16 to 20 of the publication.
-1 to Na-22 compounds and Nb-1 to Nb-12
Compound. General formula (1), general formula (2), general formula (3), general formula (4) described in Japanese Patent Application No. 7-37817.
Compounds represented by the general formulas (5), (6) and (7), specifically, 1-1 to 1 described in the same specification.
-19 compound, 2-1 to 2-22 compound, 3-1 to
Compound of 3-36, compound of 4-1 to 4-5, 5-1 to
Compounds of 5-41, compounds of 6-1 to 6-58 and 7
-1 to 7-38.

The nucleation accelerator which is particularly preferably used in the present invention is represented by the general formula (III), the general formula (IV) and the general formula (V).
It is a compound represented by these. First, the nucleation accelerator represented by the general formula (III) or the general formula (IV) will be described in detail. General formula (III)

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General formula (IV)

[0091]

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In the formula, A represents an organic group for completing the heterocycle, which may contain a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom or a sulfur atom, and the benzene ring may be condensed. . As a preferred example, A can be a 5- or 6-membered ring, and a more preferred example is a pyridine ring. B and C are alkylene,
Arylene, _{alkenylene, -SO 2 -, - SO -} , -
O -, - S -, - N (R 5) - the meanings that are configured either alone or in combination. However, R ₅ represents an alkyl group, an aryl group, or a hydrogen atom. As a preferred example, B,
Examples of C include alkylene, arylene, -O-, and -S-, which may be used alone or in combination. R
₁ and R ₂ represent an alkyl group having 1 to 20 carbon atoms and may be the same or different. The alkyl group may be substituted with a substituent, and examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom), a substituted or unsubstituted alkyl group (eg, methyl group, hydroxyethyl group, etc.), a substitution or Unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl group, etc.), substituted or unsubstituted acyl group (eg, benzoyl group, p
-Bromobenzoyl group, acetyl group, etc.), sulfo group,
Carboxy group, hydroxy group, alkoxy group (for example,
Methoxy group, ethoxy group, etc.), aryloxy group, amide group, sulfamoyl group, carbamoyl group, ureido group, unsubstituted or alkyl-substituted amino group, cyano group,
It represents a nitro group, an alkylthio group, or an arylthio group.
As a preferred example, R ₁ and R ₂ each represent an alkyl group having 1 to 10 carbon atoms. Preferred examples of the substituent include an aryl group, a sulfo group, a carboxy group, and a hydroxy group. R ₃ and R ₄ each represent a substituent, and examples of the substituent are the same as the substituents mentioned for R ₁ and R ₂ . As preferred examples, R ₃ and R ₄ have 0 to 10 carbon atoms, and specific examples thereof include an aryl-substituted alkyl group and a substituted or unsubstituted aryl group. X represents an anionic group, but X is not necessary in the case of an inner salt.
Examples of X include chlorine ion, bromine ion, iodine ion,
It represents nitrate ion, sulfate ion, p-toluenesulfonate ion, and oxalate. Next, specific compounds of the present invention are described, but are not limited thereto. Further, the compound of the present invention can be easily synthesized by a generally well-known method, and the following documents are helpful.
(Reference, Quart. Rev., 16, 163 1962).)

Specific compounds of the general formulas (III) and (IV) are shown below, but the invention is not limited thereto.

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[0095]

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[0096]

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[0097]

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Next, the nucleation accelerator represented by the general formula (V) will be described in detail. General formula (V)

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In the formula, R ₁ , R ₂ and R ₃ represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group or a heterocyclic residue, which may further have a substituent. . m represents an integer, L represents an m-valent organic group which is bonded to a P atom and its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X is linked to L. You may have. Examples of the groups represented by R ₁ , R ₂ and R ₃ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s
linear or branched alkyl groups such as ec-butyl group, tert-butyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, octadecyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group, etc. Aryl groups such as cycloalkyl groups, phenyl groups, naphthyl groups, and phenanthryl groups; allyl groups, vinyl groups, 5
An alkenyl group such as a hexenyl group; a cycloalkenyl group such as a cyclopentenyl group or a cyclohexenyl group;
Pyridyl group, quinolyl group, furyl group, imidazolyl group,
Examples of the heterocyclic residue include a thiazolyl group, a thiadiazolyl group, a benzotriazolyl group, a benzothiazolyl group, a morpholyl group, a pyrimidyl group, and a pyrrolidyl group. Examples of substituents substituted on these groups are R ₁ ,
In addition to the groups represented by R ₂ and R ₃ , halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, nitro group, 1,2,3 tertiary amino group, alkyl or aryl ether group, alkyl or aryl Examples thereof include thioether group, carbonamido group, carbamoyl group, sulfonamide group, sulfamoyl group, hydroxyl group, sulfoxy group, sulfonyl group, carboxyl group, sulfonic acid group, cyano group and carbonyl group. Examples of the group represented by L include the groups having the same meanings as R ₁ , R ₂ and R _3, and polymethylene groups such as trimethylene group, tetramethylene group, hexamethylene group, pentamethylene group, octamethylene group and dodecamethylene group. Divalent aromatic groups such as phenylene group, biphenylene group and naphthylene group, trimethylenemethyl group,
Polyvalent aliphatic groups such as tetramethylenemethyl group, phenylene-1,3,5-toluyl group, phenylene-1,2,
Examples include polyvalent aromatic groups such as 4,5-tetrayl group. Examples of the anion represented by X include halogen ions such as chlorine ion, bromine ion and iodine ion,
Carboxylate ions such as acetate ion, oxalate ion, fumarate ion, benzoate ion, p-toluenesulfonate, methanesulfonate,
Examples thereof include sulfonate ion such as butane sulfonate and benzene sulfonate, sulfate ion, perchlorate ion, carbonate ion, and nitrate ion. In the general formula (V), R ₁ , R ₂ and R ₃ are preferably groups having 20 or less carbon atoms, and aryl groups having 15 or less carbon atoms are particularly preferred.
m is preferably 1 or 2, and when m represents 1, L is preferably a group having 20 or less carbon atoms, and particularly preferably an alkyl group or an aryl group having 15 or less total carbon atoms. m is 2
The divalent organic group represented by L is preferably an alkylene group, an arylene group or a divalent group formed by combining these groups, and further, these groups and -CO-.
Group, —O— group, —NR ₄ — group (provided that R ₄ represents a hydrogen atom or a group having the same meaning as R ₁ , R ₂ and R ₃ and when a plurality of R _4's are present in the molecule, they are the same. Or may be different, and may even be bonded to each other),
It is a divalent group formed by combining a —S— group, a —SO— group, and a —SO ₂ — group. When m represents 2, L is particularly preferably a divalent group having a total carbon number of 20 or less, which is bonded to a P atom at that carbon atom. When m is an integer of 2 or more, R ₁ in the molecule, R _2, R ₃ is present in plural, but a plurality of R _1, R _2, even if R ₃ is optionally substituted by one or more identical respectively good. n is preferably 1 or 2,
X may combine with R ₁ , R ₂ , R ₃ or L to form an inner salt. Many of the compounds represented by formula (V) of the present invention are known and commercially available as reagents. As a general synthesis method, there is a method in which a phosphinic acid is reacted with an alkylating agent such as an alkyl halide or a sulfonic acid ester, or a method in which a counter anion of a phosphonium salt is exchanged by a conventional method. Specific examples of the compound represented by the general formula (V) are shown below. However, the present invention is not limited to the following compounds.

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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The nucleation accelerator of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl. It can be used by dissolving it in cellosolve or the like. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, the powder of the nucleation accelerator can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

The nucleation accelerator of the present invention may be added to any of the silver halide emulsion layer or other hydrophilic colloid layer on the silver halide emulsion layer side of the support. It is preferably added to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the nucleation accelerator of the present invention is 1 × 10 ⁻⁶ to 2 × 10 per mol of silver halide.
^-2 mol is preferable, 1 × 10 ⁻⁵ to 2 × 10 ⁻² mol is more preferable, and 2 × 10 ⁻⁵ to 1 × 10 ⁻² mol is most preferable.

The light-sensitive silver halide emulsion of the present invention may be spectrally sensitized with a sensitizing dye into blue light, green light, red light or infrared light having a relatively long wavelength. The addition amount of the sensitizing dye used in the present invention varies depending on the shape, size, etc. of the silver halide grains, but is 4 × 10 ⁻⁶ to 1 mol per mol of silver halide.
Used in the 8 × 10 ⁻³ molno range. For example, when the silver halide grain size is 0.2 to 1.3 μm, 2 × 10 ^{−7 to} 3.5 × per 1 m ² of surface area of the silver halide grain.
The addition amount range of 10 ⁻⁶ mol is preferable, and 6.5 × 10 is particularly preferable.
The addition amount range of ^{−7 to} 2.0 × 10 ⁻⁶ mol is preferable.

As the sensitizing dye, cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holoholer cyanine dye, styryl dye, hemicyanine dye, oxonol dye, hemioxonol dye and the like can be used. Useful sensitizing dyes used in the present invention are, for example, RESEARCH DISCLOS
URE Item 17643 IV-A (Dec. 1978, p. 23) and Item 1831X (Dec. 1978, p. 437) or cited therein. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, A) For an argon laser light source,
No. 62247, JP-A-2-48653, U.S. Pat.
No. 161,331, West German Patent 936,071, Simple Merocyanines described in Japanese Patent Application No. 3-189532,
B) For a helium-neon laser light source, see JP-A-50-62425, JP-A-54-18726, and JP-A-59-62426.
No. 102229, trinuclear cyanine dyes, C) L
Japanese Patent Publication No. 48 for ED light source and red semiconductor laser
-42172, 51-9609, 55-398
No. 18, JP-A-62-284343, JP-A-2-10
JP-A-59-1910 for thiacarbocyanines described in 5135 and D) infrared semiconductor laser light source.
No. 32, tricarbocyanines described in JP-A-60-80841, JP-A-59-192242 and JP-A-3-67242, and general formula (IIIa) and general formula (IIIb). -Dicarbocyanines and the like containing a quinoline nucleus are advantageously selected. These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure (Resear
ch Disclosure) Volume 176 17643 (December 1978)
(Published monthly), page 23, IV, J.

The following dyes are preferably used for the argon laser light source.

[0113]

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[0114]

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For the helium-neon light source, in addition to the above, it is represented by the general formula (I) described in Japanese Patent Application No. 4-228745, page 8, line 1 to page 13, line 4 to line 13. Particularly preferred are sensitizing dyes. Specific examples are shown below, but in addition to these, any of those described in the general formula (I) of Japanese Patent Application No. 4-228745 is preferably used.

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[0117]

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The dyes listed below are particularly preferably used for the LED light source and the infrared semiconductor laser.

[0119]

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[0120]

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The following dyes are preferably used for the infrared semiconductor laser light source.

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[0123]

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[0124]

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The sensitizing dye of the general formula (IV) described in Japanese Patent Application No. 5-201254 (page 14, line 14 to page 22, line 23) is preferably used for white light sources such as those photographed by a camera. . Specific compound examples are shown below.

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[0127]

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[0128]

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[0129]

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The halogen composition of the silver halide emulsion used in the present invention is not particularly limited, and in order to more effectively achieve the object of the present invention, silver chloride having a silver chloride content of 50 mol% or more and chlorobromide. Silver and silver chloroiodobromide are preferred. The content of silver iodide is preferably less than 5 mol%, particularly preferably less than 2 mol%.

In the present invention, the light-sensitive material suitable for high illuminance exposure such as scanner exposure and the light-sensitive material for line drawing are
Rhodium compounds are included to achieve high contrast and low fog. As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound, or a rhodium complex salt having a halogen, an amine, oxalate, etc. as a ligand, such as a hexachlororhodium (III) complex salt, a hexabromorhodium (III) complex salt, a hexaaminerhodium ( III) Complex salt, trisalathodium (II
I) Complex salts and the like can be mentioned. These rhodium compounds are
It is used by dissolving it in water or an appropriate solvent, but it is generally used to stabilize the solution of the rhodium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.), or halogenation. A method of adding an alkali (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide. The addition amount is 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ mol, preferably 5 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol, per mol of silver in the silver halide emulsion. The addition of these compounds can be appropriately carried out at each stage before the production of the silver halide emulsion grains and before the coating of the emulsion, but it is particularly preferable to add them at the time of forming the emulsion and to incorporate them into the silver halide grains. . The photographic emulsion used in the present invention is Chimie et Physique Photograp by P. Glafkides.
hique (Paul Montel, 1967), GFDufin
By Photographic Emulsion Chemistry (The Focal Pres
s, 1966), by VL Zelikman et al Making an
d Coating Photographic Emulsion (The Focal Press
Ed., 1964) and the like.

As the method of reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Method of forming grains in excess of silver ions (so-called reverse mixing method)
Can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds.
No. 08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-
Dimethyl-2-imidazolidinthione. According to the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and the silver halide used in the present invention is easy to produce. It is a useful tool for making emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016, JP-B-48-3689.
No. 0 and No. 52-16364,
A method in which the addition rate of silver nitrate or alkali halide is changed according to the grain growth rate, and a method disclosed in British Patent No. 4,242,4
No. 45 and Japanese Patent Application Laid-Open No. 55-158124, it is preferable to use a method of changing the concentration of the aqueous solution and to grow the solution quickly within a range not exceeding the critical saturation. The emulsion of the present invention is preferably a monodisperse emulsion, and the coefficient of variation is preferably 20% or less, particularly preferably 15% or less. The average grain size of the grains in the monodispersed silver halide emulsion is 0.5 μm.
m or less, and particularly preferably 0.1 μm to 0.4 μm
It is.

The silver halide emulsion of the present invention is preferably chemically sensitized. As the chemical sensitization method, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method and a noble metal sensitization method can be used, and they can be used alone or in combination. When used in combination,
For example, a sulfur sensitization method and a gold sensitization method, a sulfur sensitization method, a selenium sensitization method and a gold sensitization method, a sulfur sensitization method, a tellurium sensitization method, and a gold sensitization method are preferable.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. Known compounds can be used as the sulfur sensitizer. For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like are used. be able to. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The amount of the sulfur sensitizer to be added varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, but is preferably 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ^-5 to 10 ^-3 mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. As unstable selenium compounds, JP-B-44-15748 and 43-13489,
Japanese Patent Application Nos. 2-13097, 2-229300, and 3
Compounds described in JP-A-121798 can be used. In particular, the general formula (VIII) in Japanese Patent Application No. 3-121798.
It is preferable to use the compound represented by (IX).

The tellurium sensitizer used in the present invention is a compound which forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains. Regarding the formation rate of silver telluride in a silver halide emulsion, see Japanese Patent Application No.
It can be tested by the method described in No. 146739.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496
No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33.
No. 3819, No. 3-53693, No. 3-131598
No. 4-129787, Journal of Chemical Society Chemical Communication
(J.Chem.Soc.Chem.Commun.) 635 (1980), ibid
1102 (1979), ibid 645 (1979),
Journal of Chemical Society Perkin Transaction (J.Chem.Soc.Perkin.Trans.)
1, 191 (1980), edited by S. Patai, The Chemistry of Organic Selenium and Tellurium Campounds (The Chmistry of Or)
ganic Serenium and Tellunium Compounds), Vo 1 (1
986) and Vol 2 (1987). In particular, the compounds represented by formulas (II), (III) and (IV) in Japanese Patent Application No. 4-146739 are preferred.

The amount of the selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical ripening, and the like, but generally ranges from 10 ^-8 to 10 ^-2 mol per mol of silver halide. Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C. Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium and iridium, with gold sensitization being particularly preferred. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide.
About 10 ^-7 to 10 ^-2 mol per mol can be used. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may coexist in the process of forming silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention according to the method described in European Patent Application (EP) -293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (for example, those having different average grain sizes,
Those having different halogen compositions, those having different crystal habits, and those having different conditions of chemical sensitization) may be used in combination.

In the present invention, a silver halide emulsion particularly suitable as a reversal light-sensitive material is a silver halide containing 90 mol% or more, more preferably 95 mol% or more, and silver bromide in an amount of 0 to 10%. It is silver chlorobromide or silver chloroiodobromide containing mol%. If the ratio of silver bromide or silver iodide increases, the safety of safelight in a bright room deteriorates, or γ
Is lowered, which is not preferable.

The silver halide emulsion used in the reversal light-sensitive material of the present invention preferably contains a transition metal complex. As transition metals, Rh, Ru, Re, Os, I
r, Cr, and the like. The ligands include nitrosyl and thionitrosyl bridging ligands, halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand, selenoate ligand Cyanate, tellurocyanate, acid and aquo ligands. When an aco ligand is present, it preferably occupies one or two of the ligands.

Specifically, in order to contain a rhodium atom, a metal salt in any form such as a single salt or a complex salt can be added and added at the time of grain preparation. Examples of the rhodium salt include rhodium monochloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, and the like, but are preferably water-soluble trivalent rhodium halogen complex compounds such as hexachlororhodium (III) acid or its Salts (ammonium salt, sodium salt, potassium salt, etc.). The amount of these water-soluble rhodium salts added is in the range of 1.0 × 10 ⁻⁶ mol to 1.0 × 10 ⁻³ mol per mol of silver halide. Preferably 1.0 × 10 ⁻⁵ mol
1.0 × 10 ⁻³ mol, particularly preferably 5.0 × 10 ⁻⁵ mol to 5.0 × 10 ⁻⁴ mol.

The following transition metal complexes are also preferable. 1 [Ru (NO) Cl ₅ ] ^-2 2 [Ru (NO) ₂ Cl ₄ ] ^-1 3 [Ru (NO) (H ₂ O] Cl ₄ ] ^-1 4 [Ru (NO) Cl ₅ ] ^-2 5 [Rh (NO) Cl _5] ^-2 6 [Re (NO) CN _5] ^-2 7 [Re (NO) ClCN _4] ^-2 8 [Rh (NO) ₂ Cl _4] ^-1 9 [Rh (NO ) (H ₂ O) Cl ₄ ] ^-1 10 [Ru (NO) CN ₅ ] ^-2

11 [Ru (NO) Br ₅ ] ^-2 12 [Rh (NS) Cl ₅ ] ^-2 13 [Os (NO) Cl ₅ ] ^-2 14 [Cr (NO) Cl ₅ ] ^-3 15 [Re (NO) Cl ₅ ] ^-1 16 [Os (NS) Cl ₄ (TeCN)] ^-2 17 [Ru (NS) I ₅ ] ^-2 18 [Re (NS) Cl ₄ (SeCN)] ^-2 19 [Os (NS) Cl (SCN) ₄ ] ^-2 20 [Ir (NO) Cl ₅ ] ^-2

Next, the compound represented by the general formula (II) will be described in detail. General formula (II)

[0144]

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In the formula, Y and Z may be the same or different and each is N or CR ² (R ² represents an alkyl group or an aryl group), R ¹ is —SO ₃ M, —COOM, —OH, —NH.
_{^{SO 2 R 3, -SO 2 NR}} 3 R 4 and -NR ⁵ CON
It represents an alkyl group, an aryl group or a heterocyclic group substituted with at least one selected from the group consisting of R ³ R ⁴ or a group in which an alkyl group, an aryl group or a heterocyclic group is formed via a linking group. R ³ , R ⁴ and R ⁵ may be the same or different and each is a hydrogen atom or a carbon number of 1 to 4.
Represents a lower alkyl group. M represents a hydrogen atom, an alkali metal, a quaternary ammonium and a quaternary phosphonium.

Specific examples of the alkyl group represented by R ¹ include linear, branched or cycloalkyl groups having 1 to 20 carbon atoms (eg, methyl group, propyl group, hexyl group, dodecyl group, isopropyl group, etc.). Specific examples of the cycloalkyl group having 1 to 20 carbon atoms (for example, cyclopropyl group, cyclohexyl group, etc.) and the aryl group include 6 to 2 carbon atoms.
0 aryl group (eg, phenyl group, naphthyl group, etc.),
The heterocyclic group is specifically one or more nitrogen, oxygen or a 7-membered heterocyclic ring, and also includes those forming a condensed ring at an appropriate position (eg, pyridine ring, quinoline ring, Pyrimidine ring, isoquinoline ring, etc.).
The alkyl group, aryl group and heterocyclic group may be further substituted with a substituent other than those listed above, specifically, a halogen atom (F, Cl, Br etc.), an alkyl group (methyl group, ethyl group). Group), an aryl group (phenyl group,
p-chlorophenyl group, etc.) alkoxy group (methoxy group,
Methoxyethoxy group, etc.), aryloxy group (phenoxy group, etc.), sulfonyl group (methanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group (unsubstituted carbamoyl group, diethylcarbamoyl group, etc.), amide group (acetamido group, Benzamide group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, etc.),
Aryloxycarbonylamino group (phenoxycarbonylamino group, etc.), alkoxycarbonyl group (methoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), cyano group, nitro group, amino group (unsubstituted amino group, dimethylamino) Groups), alkylsulfinyl groups (methoxysulfinyl groups, etc.), arylsulfinyl groups (phenylsulfinyl groups, etc.), alkylthio groups (methylthio groups, etc.), and arylthio groups (phenylthio groups, etc.), and these substituents May be substituted by two or more, and when two or more are substituted, they may be the same or different. Further, as the above-mentioned linking group which may be contained in R ₁ , —S—, —O—, —N (R ₃ )
-, - CO -, - SO -, - SO 2 -, - SO 2 N (R
_{3) -, - CON (R} 3) -, - COO- is preferred.
Here, R ₃ has the same meaning as the above-mentioned —NHSO ₂ R _{3 and the} like.

The following can be mentioned as specific examples of R ₁ having a linking group.

[0148]

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The alkyl group and aryl group represented by R ₂ include those each having a substituent, and examples of the substituent include the same substituents as R ₁ .

Among the compounds represented by the general formula (II), those particularly preferred are those represented by the general formula (VI). General formula (VI)

[0151]

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R _{5 in the} general formula (VI) is at least one —C
_{OOM, -SO 3 M, -OH,} -NHSO 2 R 3, -S
It represents a phenyl group substituted with O ₂ NR ₃ R ₄ or —NR ₃ CONR ₃ R ₄ , and this phenyl group may be further substituted with another substituent. Where -COO
_{M, -SO 3 M, -OH,} -NHSO 2 R 3, -SO 2
NR ₃ when R ₄ and -NR ₃ CONR ₃ R ₄ there are two or more may be the same or different, -COOM, -
SO ₃ M is particularly preferred. M has the same meaning as that represented by the general formula (II). Specific examples of the compound represented by formula (II) used in the present invention are shown below, but the scope of the present invention is not limited to this compound.

[0153]

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[0154]

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[0155]

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[0156]

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The compound represented by the general formula (II) can be easily synthesized by a method using isothiocyanate as a starting material, as is well known. The following patents that describe the synthetic method that serves as a reference;
Describe the literature. US Pat. Nos. 2,585,388 and 2,5
41,924, Japanese Examined Patent Publication No. 42-21842, U.S. Pat. No. 3,266,897, British Patent 1,275,701.
No. 56-118846, DABerges et al.,
"Journal of Heterocyclic Chemistry" Volume 15 Issue 981
(1978), "The Chemistry of Heterocyclic Chemistr
y "Imidazole and Derivatives part I, 336-339
Page, Chemical Abstract 58, 7921 (1963), page 394, E.
Hoggarth "Journal of Chemical Society" 1949, 11
Pages 60-1167, SR Organic W. Karo "Organic Functiona"
l Group Preparation "Academic Press (1968), 312
~ P. 315, II Kovtunovskaya Lovshine Tr.Ukr.Ins
t.Eksperim Endokrinol Vol. 18, p. 345 (1961), M. Cha.
mdon et al., Bull. Chem. Fr., 723 (1954), DAShirley,
DWAlley, J. Amer. Chem. Soc., 79, 4922 (1957), A. Woh
l, w.marckwald, German Chemical Society (Ber.) Vol. 22, 568 (188
9). The compound represented by the general formula (I) is used in the same amount as a usual additive, but preferably 5 mg to 1 g /
It is used in liters, more preferably 10 mg to 500 mg / liter.

The silver halide light-sensitive material of the present invention is developed with a developing solution containing a dihydroxybenzene type developing agent as a developing agent and an auxiliary developing agent exhibiting superadditivity therewith. In the development processing, a usual automatic development processor can be used. The developing solution filled in the development processing tank at the start of development is called a development starting solution (mother solution), and the developing solution replenished in the development processing tank at the time of continuous development is called a development replenishing solution. In the present invention, both the development starter solution and the development replenisher solution contain, as a developing agent, a dihydroxybenzene type developing agent and an auxiliary developing agent exhibiting superadditivity with the dihydroxybenzene type developing agent.

As the dihydroxybenzene type developing agent used in the present invention, there are hydroquinone, chlorohydroquinone, isopropylhydroquinone, methylhydroquinone, hydroquinone monosulfonate and the like, and hydroquinone is particularly preferable. As the auxiliary developing agent showing superadditivity with the dihydroxybenzene type developing agent, 1-
There are phenyl-3-pyrazolidones and p-aminophenols. Therefore, in the present invention, a combination of a dihydroxybenzene-based developing agent and 1-phenyl-3-pyrazolidones or a combination of a dihydroxybenzene-based developing agent and p-aminophenols is preferably used. The developing agents of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4. -Hydroxymethyl-3-pyrazolidone and the like. The p-aminophenol-based developing agents used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-
Hydroxyphenyl) glycine, etc., among which N
-Methyl-p-aminophenol is preferred. The dihydroxybenzene type developing agent is usually 0.05 to 0.8 mol /
It is preferably used in an amount of 1 liter, but in the present invention, it is particularly preferably used in an amount of 0.23 mol / liter or more. More preferably, 0.23 to 0.6 mol /
It is in the liter range. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.23.
~ 0.6 mol / liter, more preferably 0.23 ~
0.5 mol / liter, the latter 0.06 mol / liter or less, more preferably 0.03 mol / liter to 0.
It is preferably used in an amount of 003 mol / l.

In the present invention, both the development initiating solution and the development replenishing solution have the property that "the pH increase when 0.1 mol of sodium hydroxide is added to 1 liter of the solution is 0.25 or less". It is necessary. The method of confirming that the development starter solution or development replenisher used has this property is as follows.
Is adjusted to 10.5, and then 0.1 mol of sodium hydroxide is added to 1 liter of this solution, and the pH value of the solution at this time is measured. It is determined that it has the property. In the present invention, it is particularly preferable to use a development starter solution and a development replenisher solution which have a pH value increase of 0.2 or less when the above test is carried out.

As a method for imparting the above-mentioned properties to the development initiating solution and the development replenishing solution, it is preferable to use a buffer.
Examples of the buffer include carbonates, boric acid described in JP-A-62-186259, sugars described in JP-A-60-93333 (eg, saccharose), oximes (eg, acetoxime), and phenols (eg, 5 -Sulfosalicylic acid), tertiary phosphates (e.g., sodium salts, potassium salts) and the like, preferably carbonates and boric acid. The amount of buffer, especially carbonate used, is preferably
0.5 mol / liter or more, particularly 0.5 to 1.5 mol /
Liters.

In the present invention, the pH of the development initiating solution is 9.0 to 11.0, particularly preferably 9.5 to 1.
It is in the range of 0.7. The pH of the developer replenisher and the pH of the developer in the developing tank during continuous processing are also in this range. p
As the alkali agent used for setting H, a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used.

When processing 1 square meter of the silver halide photographic light-sensitive material, the replenisher amount of the developing solution is 225 ml or less, preferably 225 to 30 ml, particularly 1
80 to 50 ml. The development replenisher may have the same composition as the development start solution, or may have a higher concentration of components consumed in development than the start solution.

Additives (eg, preservatives) usually used in the developing solution (both the development starting solution and the developing replenishing solution are collectively referred to as a developing solution hereinafter) for developing the light-sensitive material in the present invention. , A chelating agent). Examples of preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. 0.2 for sulfite
It is used in an amount of 0 mol / liter or more, particularly 0.3 mol / liter or more, but if added in an excessively large amount, it causes silver stain in the developing solution, so the upper limit is preferably 1.2 mol / liter. Particularly preferably, it is 0.35 to 0.7 mol / liter. As a preservative for a dihydroxybenzene-based developing agent, a small amount of an ascorbic acid derivative may be used in combination with sulfite. Here, the ascorbic acid derivative includes ascorbic acid, its stereoisomer, erythorbic acid, and alkali metal salts (sodium and potassium salts) thereof. It is preferable to use sodium erythorbate in terms of material cost. The addition amount is 0.03 to molar ratio based on the dihydroxybenzene type developing agent.
The range of 0.12 is preferable, and particularly preferably 0.05 to
It is in the range of 0.10. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Additives other than those mentioned above include
Development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole or its derivatives; mercapto Compounds, indazole compounds, benzotriazole compounds, and benzimidazole compounds may be included as antifoggants or black pepper inhibitors. Specifically, 5-nitroindazole,
5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5- Nitrobenztriazole, 4
-[(2-Mercapto-1,3,4-thiadiazole-
Examples thereof include sodium 2-yl) thio] butanesulfonate, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, and 2-mercaptobenzotriazole. The amount of these antifoggants is usually 0.01 to 10 mmol, more preferably 0.1 to 2 mmol, per liter of developer.

Further, various organic / inorganic chelating agents can be used in combination in the developer of the present invention. As the inorganic chelating agent, sodium tetrapolyphosphate, sodium hexametaphosphate or the like can be used. On the other hand, as the organic chelating agent, organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be mainly used. Examples of the organic carboxylic acids include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, succinic acid, acelineic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. , Itaconic acid, malic acid, citric acid, tartaric acid and the like, but are not limited thereto.

Examples of aminopolycarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid. Acetic acid,
Triethylenetetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diamine tetraacetic acid, and others, JP-A-52-25632, and JP-A-55-67
Nos. 747, 57-102624, and JP-B-53-
Compounds described in, for example, Japanese Patent No. 40900 can be exemplified.

As the organic phosphonic acid, US Pat.
Nos. 4454 and 3794591, and West German Patent Publication 2
227639 and the like, hydroxyalkylidene-diphosphonic acid and Research Disclosure (Research
Disclosure) Volume 181, Item 18170 (1979)
May, 2002) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid. In addition, the above Research Disclosure 18170, JP-A-57-208554 and 54- 61125, 5
Examples thereof include compounds described in JP-A Nos. 5-29883 and 56-97347.

Organic phosphonocarboxylic acids include those disclosed in JP-A Nos. 52-102726, 53-42730, and 54.
No. 121127, No. 55-4024, No. 55-40
No. 25, No. 55-126241, No. 55-65955.
No. 55-69556, and the above-mentioned Research Disclosure 18170. These chelating agents may be used in the form of an alkali metal salt or an ammonium salt.

Further, various organic / inorganic chelating agents can be used in combination in the developer of the present invention. As the inorganic chelating agent, sodium tetrapolyphosphate, sodium hexametaphosphate or the like can be used. On the other hand, as the organic chelating agent, organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be mainly used. Examples of the organic carboxylic acids include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, succinic acid, acelineic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. , Itaconic acid, malic acid, citric acid, tartaric acid and the like, but are not limited thereto.

Examples of aminopolycarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid. Acetic acid,
Triethylenetetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diamine tetraacetic acid, and others, JP-A-52-25632, and JP-A-55-67
Nos. 747, 57-102624, and JP-B-53-
Compounds described in, for example, Japanese Patent No. 40900 can be exemplified.

As the organic phosphonic acid, US Pat.
Nos. 4454 and 3794591, and West German Patent Publication 2
227639 and the like, hydroxyalkylidene-diphosphonic acid and Research Disclosure (Research
Disclosure) Volume 181, Item 18170 (1979)
May, 2002) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid. In addition, the above Research Disclosure 18170, JP-A-57-208554 and 54- 61125, 5
Examples thereof include compounds described in JP-A Nos. 5-29883 and 56-97347.

Organic phosphonocarboxylic acids include those disclosed in JP-A Nos. 52-102726, 53-42730 and 54.
No. 121127, No. 55-4024, No. 55-40
No. 25, No. 55-126241, No. 55-65955.
No. 55-69556, and the above-mentioned Research Disclosure 18170. These chelating agents may be used in the form of an alkali metal salt or an ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-1 mol per liter of developer.
It is 10 ^-3 to 1 × 10 ^-2 mol.

Further, as a silver stain preventing agent in a developing solution, JP-A-56-24347, JP-B-56-46585,
The compounds described in JP-B-62-2849 and JP-A-4-362942 can be used. Further, compounds described in JP-A-61-267759 can be used as a dissolution aid. Further, if necessary, a color tone agent, a surfactant,
It may contain an antifoaming agent, a hardening agent and the like. The developing temperature and time are interrelated and are determined in relation to the total processing time. Generally, the developing temperature is about 20 ° C to about 50 ° C, preferably 25 to 45 ° C, and the developing time is 5 seconds to 2 seconds. Minutes, preferably 7 seconds to 1 minute 30 seconds.

For the purpose of transporting the treatment liquid, packaging material cost, space saving and the like, it is preferable to concentrate the treatment liquid and dilute it before use. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer.

The fixer used in the fixing step is sodium thiosulfate, ammonium thiosulfate, tartaric acid if necessary,
An aqueous solution containing citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanic acid, tyrone, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid. From the viewpoint of recent environmental protection, it is preferable that boric acid is not contained.
As the fixing agent of the fixing solution used in the present invention, sodium thiosulfate, ammonium thiosulfate and the like are used, and ammonium thiosulfate is preferable from the viewpoint of the fixing speed, but sodium thiosulfate may be used from the viewpoint of recent environmental protection. . The use amount of these known fixing agents can be appropriately changed and is generally about 0.1 to about 2 mol / liter. Particularly preferably, it is 0.2 to 1.5 mol / l.
If desired, the fixer may include a hardening agent (eg, water-soluble aluminum compound), preservative (eg, sulfite, bisulfite), pH buffer (eg, acetic acid), pH adjuster (eg,
(Ammonia, sulfuric acid), a chelating agent, a surfactant, a wetting agent, and a fixing accelerator. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene-based surfactants, and JP-A-57-6.
The amphoteric surfactants described in Japanese Patent No. 740 can be used.
Further, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of fixing accelerators include JP-B-45-35754, 58-122535 and 58.
-122536, thiourea derivatives, alcohols having a triple bond in the molecule, U.S. Pat. No. 4,126,45.
Thioether compounds described in JP-A No. 4-22986
Examples thereof include mesoionic compounds described in No. 0, and compounds described in JP-A-2-44355 may be used. Examples of the pH buffering agent include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, oxalic acid citric acid, maleic acid, glycolic acid and adipic acid, and inorganic buffers such as boric acid, phosphate and sulfite. Agents can be used. Acetic acid, tartaric acid, and sulfite are preferably used. PH here
The buffer is used for the purpose of preventing the pH of the fixing agent from rising due to the carry-in of the developing solution, and is 0.01 to 1.0 mol / liter,
More preferably, about 0.02-0.6 mol / liter is used. The pH of the fixing solution is preferably 4.0 to 6.5, particularly preferably 4.5 to 6.0. Further, as the dye elution accelerator, the compounds described in JP-A No. 64-4739 can also be used.

As the hardening agent in the fixing solution of the present invention, there are water-soluble aluminum salts and chromium salts. A preferred compound is a water-soluble aluminum salt, such as aluminum chloride, aluminum sulfate, potassium alum. A preferable addition amount is 0.01 mol to 0.2 mol / l, more preferably 0.03 to 0.08 mol / l. Fixing temperature is
The fixing time is 5 seconds to 1 minute, preferably 7 seconds to 50 seconds at about 20 ° C to about 50 ° C, preferably 25 to 45 ° C. The replenishing amount of the fixing solution is 600 ml / per processing amount of the light-sensitive material.
m ² or less, especially 500 ml / m ² or less, further 300 ml
/ M ² or less is preferable.

The light-sensitive material which has been developed and fixed is then washed with water or stabilized. In the washing or stabilizing treatment, the washing water amount is usually ² m ² per m ^{2 of the} silver halide photosensitive material.
It is performed at 0 liters or less, and a replenishment amount (0 liters or less
In other words, it can also be carried out by washing with water. That is, not only water saving processing can be performed, but also piping for installing the automatic processing machine can be eliminated. As a method for reducing the replenishing amount of washing water, a multi-stage countercurrent method (for example, 2
Stage, three stage, etc.) are known. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in the normal direction, that is, the processing solution which is not stained with the fixing solution is sequentially contacted, so that the efficiency is further improved. Washing is performed. When the washing with water is carried out with a small amount of water, JP-A-63-18
It is more preferable to provide a washing tank for a squeeze roller and a crossover roller described in JP-A Nos. 350 and 62-287252. Alternatively, various oxidizing agents may be added or a filter may be combined to reduce the pollution load which is a problem when washing with a small amount of water. Further, part or all of the overflow liquid from the washing or stabilizing bath produced by replenishing the water subjected to the antifungal means to the washing or stabilizing bath by the method of the present invention according to the treatment is disclosed in 23
As described in JP-A No. 5133, it can be used for a processing solution having a fixing ability which is a preceding processing step. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent unevenness of water bubbles which are easily generated at the time of washing with a small amount of water and / or to prevent a treatment agent component adhering to a squeeze roller from being transferred to a treated film. Good. Further, in order to prevent contamination by the dye eluted from the photosensitive material, JP-A-63-16345
The dye adsorbent described in No. 6 may be installed in a washing tank. In addition, a stabilization process may be performed following the water washing process,
Examples thereof include JP-A-2-201357 and JP-A-2-132.
No. 435, No. 1-102553, JP-A-46-444.
A bath containing the compound described in No. 46 may be used as a final bath of the light-sensitive material. If necessary, this stabilizing bath may also contain a metal compound such as an ammonium compound, Bi, or Al, a fluorescent brightener, various chelating agents, a membrane pH regulator, a hardening agent, a bactericide, a fungicide, an alkanolamine, or a surfactant. Agents can also be added. The water used in the washing step or the stabilization step includes tap water, deionized water, halogen, ultraviolet sterilizing lamp, and water sterilized by various oxidizing agents (ozone, hydrogen peroxide, chlorate, etc.). It is preferable to use, and washing water containing the compounds described in JP-A-4-39652 and JP-A-5-241309 may be used. Washing or stabilizing bath temperature and time are 0-5
0 ° C. and 5 seconds to 2 minutes are preferred.

The treatment liquid used in the present invention is disclosed in JP-A-61-161.
It is preferable to store in a packaging material having low oxygen permeability described in No. 73147. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The roller transport type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and is simply referred to as a roller transport type processor in this specification. The roller transport type processor has four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. . Four steps of a stabilization step may be used instead of the washing step.

It is also possible to supply the components of the developing solution or fixing solution, excluding water, in the form of a solid, and dissolve them in a predetermined amount of water before use to use them as the developing solution or fixing solution. The treating agent having such a form is called a solid treating agent. The solid processing agent is
Powders, tablets, granules, powders, lumps or pastes are used, and the preferred form is JP-A-61-259921.
The form or tablet described in No. The tablet manufacturing method is
For example, JP-A-51-61837 and JP-A-54-15503.
No. 8, No. 52-88025, British Patent Nos. 1,213,8.
No. 08, etc., and the granule-treating agent can be produced by, for example, JP-A Nos.
109043, 3-39735 and 3-397.
It can be produced by a general method described in No. 39, etc. Further, the powder treating agent is disclosed in, for example, JP-A-54-133332.
And British Patent Nos. 725,892 and 729,862, and German Patent No. 3,733,861.

The bulk density of the solid processing agent is 0.5 to 6.0 g / from the viewpoint of its solubility and the effect of the object of the present invention.
cm ³ is preferable, especially 1.0 to 5.0 g / cm
³ is preferable.

In the preparation of the solid processing agent, at least two mutually reactive particulate materials among the materials constituting the processing agent and at least one interposition of a material inert to the reactive material are used. It is also possible to employ a method in which the reactive substances are arranged in layers so as to form layers separated by the separation layer, a vacuum-packable bag is used as the packaging material, and the bag is evacuated and sealed. As used herein, the term inert means that the substances do not react under normal conditions in the package when they are in physical contact with each other, or if any reaction is not significant. The inert substance, apart from being inert to the two mutually reactive substances, need only be inert in the intended use of the two reactive substances. Furthermore, an inert substance is a substance that is used simultaneously with two reactive substances. For example, since hydroquinone and sodium hydroxide react with each other in a developing solution when they come into direct contact, they can be stored in a package for a long period of time by using sodium sulfite or the like as a separation layer between hydroquinone and sodium hydroxide in vacuum packaging. Further, hydroquinone or the like is formed into a briquette to reduce the contact area with sodium hydroxide, so that the preservability is improved and the mixture can be used. Used as packaging materials for these vacuum packaging materials are bags made from a laminate of inert plastic film, plastic material and metal foil.

There are no particular restrictions on various additives used in the light-sensitive material of the present invention, and for example, those described in the following sections can be preferably used. Item 1) Nucleation accelerator A compound represented by the general formula (I), (II), (III), (IV), (V) or (VI) described in Japanese Patent Application No. 4-237366. JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10, general formulas (II-m) to (II-p) and compound examples II-1 to II-22; Compounds described in JP-A-1-179939. 2) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to lower right column, line 4, JP-A-2-103536, page 16, lower right column, line 3 to page 17, lower left Column 20, line 20. Further, spectral sensitizing dyes described in JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, Japanese Patent Application Nos. 3-189532 and 3-411046. 3) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7, and JP-A-2-18542, page 2, lower left column, line 13 to line 4 Line 18 in the lower right column of the page. 4) Antifoggants JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, and JP-A 1-237538. Thiosulfinic acid compounds described in the official bulletin. 5) Polymer latex: JP-A-2-103536, page 18, lower left column, lines 12 to 20. 6) Compound having an acid group From page 6, lower right column, line 6 to page 19, upper left column, line 1 of JP-A-2-103536. 7) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column, 15 plasticizer line to page 19, upper right column, 15th line. 8) Hardener From page 5, right upper column, line 5 to line 17, JP-A-2-103536. 9) Dyes Dyes on page 17, right lower column, lines 1 to 18 of JP-A-2-103536, solid dyes described in JP-A-2-29438 and JP-A-3-185773. 10) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 11) Black spot inhibitors Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 12) Redox compound A compound represented by the general formula (I) of JP-A-2-301743 (especially, compound examples 1 to 50), and a compound represented by the general formula (3) of JP-A-3-174143, pp. 3 to 20: (R-1), (R-2), (R-3), compounds described in Compound Examples 1 to 75, and further described in Japanese Patent Application Nos. 3-69466 and 3-15648. 13) Monomethine compounds Compounds of the general formula (II) described in JP-A-2-287532 (especially compound examples II-1 to II-26). 14) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to pages 12, page 12, lower left column, and EP452772A.

[0184]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

The following nucleating agents were used as Comparative Compounds A and B of the nucleating agent of the present invention.

[0186]

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Example 1 <Preparation of silver halide photographic light-sensitive material> Emulsion preparation Emulsion A was prepared by the following method. [Emulsion A] An aqueous solution of silver nitrate, potassium bromide, sodium chloride and K corresponding to 3.5 × 10 ^-7 mol per mol of silver.
₃ IrCl ₆ and K ₂ Rh equivalent to 2.0 × 10 ⁻⁷ mol
A halogen salt aqueous solution containing (H ₂ O) Cl ₅ , sodium chloride, and a gelatin aqueous solution containing 1,3-dimethyl-2-imidazolidinthione were added by stirring by a double jet method to give an average particle size of 0.25 μm. Silver chlorobromide grains having a silver chloride content of 70 mol% were prepared.

Thereafter, the product was washed with water by a flocculation method according to a conventional method, 40 g of gelatin was added per 1 mol of silver, 7 mg of sodium benzenethiosulfonate and 2 mg of benzenesulfinic acid were added per 1 mol of silver, and the pH was adjusted to 6.0. The pAg was adjusted to 7.5, and 2 mg of sodium thiosulfate and 4 mg of chloroauric acid were added per 1 mol of silver, and chemical sensitization was performed at 60 ° C. to obtain optimum sensitivity. Thereafter, 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer, and 100 mg of proxel was further added as a preservative. Each of the obtained particles has an average particle size of 0.25 μm.
m, silver chlorobromide cubic grains having a silver chloride content of 70 mol%. (Coefficient of variation 10%)

Preparation of Coating Sample On a polyethylene terephthalate film support having a moisture-proof layer undercoat containing vinylidene chloride, from the support side,
Samples were prepared by applying the layers sequentially to form a UL layer, an EM layer, a PC layer, and an OC layer. The preparation method and application amount of each layer are shown below.

(UL layer) To a gelatin aqueous solution, a dispersion of 30 wt% of polyethyl acrylate with respect to gelatin was added and coated so as to have gelatin of 0.5 g / m ² .

[0191] in (EM layer) above emulsions A, the following compound as a sensitizing dye (S-1) per mole of silver 5 × 10 ^-4 mol, the 5 × 10 ^-4 mol was added (S-2), further 3 × 10 ^-4 mol of mercapto compound represented by the following (a), 4 × 10 ^-4 mol of mercapto compound represented by (b), and 4 × 10 ^-4 mol of (c) per 1 mol of silver Triazine compound, 2 × 10 ⁻³ mol of 5-chloro-8-hydroxyquinoline, 5 × 10 ⁻⁴ mol of the following compound (p), and 4 × 10 ⁻⁴ mol of the following compound (A) as a nucleation accelerator. Was added. Further, 100 mg of hydroquinone and 30 mg / m ^{2 of} N-oleyl-N-methyltaurine sodium salt were added.
Added as applied. Next, the nucleating agent (hydrazine derivative) shown in Table 2 was 1 × 10 ⁻⁵ mol / m ² , the water-soluble latex shown in (d) was 200 mg / m ² , and the polyethyl acrylate latex was 200 mg / m ^2. , Styrene / butadiene = 37/63 (wt%) in the core, styrene / 2-acetoxyethyl methacrylate = 84/16 (wt%) in the shell, and core / shell ratio = 50/50
Of core-shell latex of 600 mg / m ² , colloidal silica having an average particle diameter of 0.02 μm of 200 mg / m ² ,
Further, as a hardener, 1,3-divinylsulfonyl-2-
200 mg / m ^{2 of} propanol was added. Solution pH
Was adjusted to 5.65 with acetic acid. They were coated so that the coating silver amount was 3.5 g / m ² (gelatin coating amount 1.3 g / m ² ).

(PC layer) A dispersion of 50 wt% ethyl acrylate in gelatin aqueous solution, and
The following surfactant (w) was added at 5 mg / m ² , and 1,5-dihydroxy-2-benzaldoxime was added at 10 mg / m ² , and gelatin was applied at 0.5 g / m ² . .

(OC layer) Gelatin 0.5 g / m ² , amorphous SiO ₂ matting agent 4 having an average particle size of about 3.5 μm 4
0 mg / m ² , methanol silica 0.1 g / m ² , polyacrylamide 100 mg / m ² and silicone oil 2
0 mg / m ² and 5 mg / m ^{2 of} a fluorosurfactant represented by the following structural formula (e) as a coating aid and 100 mg / m ² of sodium dodecylbenzenesulfonate were coated.

[0194]

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These coated samples have a back layer and a back protective layer having the following compositions. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40 mg / m ²

[0196]

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SnO ₂ / Sb (weight ratio 90/10, average particle size 0.20 μm) 200 mg / m ² dye Mixture of dye [a], dye [b] and dye [c] dye [a] 70 mg / m ² Dye [b] 70 mg / m ² Dye [c] 90 mg / m ²

[0198]

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[Back protective layer] Gelatin 0.8 mg / m ² polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² p-dodecylbenzenesulfonic acid Sodium 15 mg / m ² Sodium acetate 40 mg / m ²

Table 2 shows the nucleating agent species and sample No. The sample is passed through an interference filter with a peak at 488 nm,
It was exposed through a step wedge with a xenon flash light having an emission time of 10 ^-5 sec for evaluation of photographic performance. In addition,
The film surface pH on the side having the emulsion phase was 5.6, and the swelling ratio ((swollen film thickness / dry dry film thickness) × 100) was 100.

The samples were evaluated by the change in photographic property by a running test. As the running condition, 100 sheets of a large-sized paper (50.8 cm × 60.1 cm) half-exposed on one day were processed and continuously operated for 1 week.
As an automatic developing machine, FG-680A manufactured by Fuji Photo Film Co., Ltd. was used under the conditions of 35 ° C. and 30 ″ (developing time).

The compositions of the developing solution and the fixing solution are shown below. (Developer composition) Potassium hydroxide 40.0 g Diethylenetriamine-pentaacetic acid 2.0 g Potassium carbonate 60.0 g Sodium metabisulfite 70.0 g Potassium bromide 7.0 g Hydroquinone 40.0 g 5-Methylbenzotriazole 0.35 g 4- Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.50 g 2-mercaptobenzimidazole-5-sulfonic acid sodium salt 0.30 g sodium erythorbate 6.0 g diethylene glycol 5.0 g potassium hydroxide and water is added. Add 1 liter and adjust pH to 10.65. 1 liter

The test developers shown in Table 1 were prepared based on the above developers.

[0204]

[Table 1]

(Fixer Formulation) Ammonium thiosulfate 360.0 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Sodium gluconate 6.6 g Aluminum sulfate 25.3 g pH (adjusted with sulfuric acid or sodium hydroxide) 4.85 Water was added to 3 liters The fixer replenishment rate was 260 ml / m ² .

The photographic property was evaluated as follows. As an index (gradation) indicating the contrast of an image, a point of fog + density 0.1 to a point of fog + density 3.0 of the characteristic curve is connected by a straight line, and the slope of this straight line is expressed as a gamma value. That is, gamma (gradation) = (3.0-0.1) /
[Log (exposure amount giving density 3.0)-(density 0.1
Exposure amount) which gives a higher gamma value, indicating that the higher the gamma value, the harder the photographic characteristics. As a graphic arts photosensitive material, gamma is preferably 10 or more, and more preferably 15 or more. The sensitivity is
For each sample, the reciprocal of the exposure amount required to obtain a density of 1.5 when treated with a new solution was set to 100, and the value after running was shown as a relative value. 95 to 1 as a relative value
05 is desirable.

The development unevenness was evaluated on a scale of 5 on the condition that no development unevenness was found on the film, "5", and development unevenness on the entire surface of the film was "1". "4" has uneven development in a very small part of the film, which is an acceptable level for practical use, but "3" or less is not practical. The uneven development was carried out by using the unexposed light-sensitive material of each sample at the end of running. Table 2 shows the values of the nucleating agent type and the replenishing amount, and the results of running and development unevenness.

[0208]

[Table 2]

As is clear from Table 2, in the sample using the nucleating agent of Comparative Example, the gradation becomes soft when the amount of replenishment is reduced and running, and the sensitive material becomes NG level. For samples using the nucleating agent of the invention, even with low replenishment,
The change in sensitivity and gradation was small, and a favorable result was obtained. In addition, even in the sample using the nucleating agent of the present invention, if the developing solutions A and D of Comparative Examples are used, development unevenness occurs or the photographic properties are greatly affected. When used, the result was that the unevenness in processing and the effect on photographic properties were small. Example 2 <Preparation of silver halide photographic light-sensitive material> Emulsion preparation Emulsion B was prepared by the following method. [Emulsion B] Emulsion except that 1 mg of selenium sensitizer of the following structural formula per mole of silver, 1 mg of sodium thiosulfate and 4 mg of chloroauric acid were added and chemically sensitized at 60 ° C. to obtain an optimum sensitivity. A was adjusted in the same manner as in A.

[0210]

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Preparation of Coating Sample Instead of the sensitizing dye of the EM layer of Example 1, the following compound (S-3) was added in an amount of 2.1 × 10 ⁻⁴ mol per mol of silver to prepare an emulsion for the EM layer. A sample was prepared in the same manner as in Example 1 except that Emulsion B was used.

[0212]

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(1) Exposure and Development Treatment The above sample was exposed to xenon flash light having an emission time of 10 ⁻⁶ sec through a step wedge through an interference filter having a peak at 633 nm.

The method for producing a solid developer is as follows. A container made of high-density polyethylene (average wall thickness = 500 μm, partially 200-1000 μm) is packed with 10 liters of developing components as a working solution in solid form. It was At this time, the components were mixed and then filled in a container.

Next, the composition of the developer is shown below. Sodium hydroxide (beads) 99.5% 11.5g Potassium sulfite (bulk powder) 71.8g Sodium sulfite (bulk powder) 35.0g Potassium carbonate (bulk powder) 62.0g Hydroquinone (briquette) 40.0g Collectively Briquette Diethylenetriamine Pentaacetic acid 2.0 g 5-Methylbenzotriazole 0.35 g 4-Hydroxymethyl-4-methyl 1.50 g -1-Phenyl-3-pyrazolidone 2-Mercaptobenzimidazole 0.30 g-5-Sulfonate sodium erythorbate 6 0.0 g Potassium bromide 6.6 g Based on this formulation, the compounds shown in Table 1 were added to prepare a test developer. The pH when this formulation was dissolved in up to 1 liter of water was 10.65.

Here, in the raw material form, the bulk powder was used as it was as a general industrial product, and the beads of the alkali metal salt were commercial products. If the raw material form is briquette, it is pressed and compressed using a briquetting machine to give an irregular length of 4 to
A rugby ball-shaped shape of about 6 mm was prepared, crushed and used. For the minor components, each component was blended before briquetting.

The fixing solution was made of high-density polyethylene in the following formulation for both the solid agent portion and the liquid agent portion (wall thickness average = 500 μm,
The width used was one filled in a container having a width of 200 to 1000 μm. The volume of the solution after dissolution is 10 liters, and the pH =
It was 4.85. The replenisher rate of the fixing solution was 260 ml / m ² .

<Solid Agent Part> Ammonium thiosulfate 1300 g Sodium acetate 400 g Sodium metabisulfite 200 g <Liquid agent part> Aluminum sulfate (27%) 300 g Sulfuric acid (75%) 30 g Sodium gluconate 20 g EDTA 0.3 g Citric acid 40 g Solid agent part Are mixed and filled.

The photographic properties and running properties were evaluated in the same manner as in Example 1. As a result, the same results as in Example 1 were obtained, and the nucleating agent of the present invention has excellent running properties.
By processing with a developer containing the compound of the general formula (II) of the present invention, uneven development could be improved without impairing photographic properties.

Example 3 <Emulsion preparation> Sodium chloride kept at 38 ° C. and 3 × 10 ⁻⁵ mol of sodium benzenethiosulfonate per mol of silver, 5 × 10 ⁻³ mol of 4-hydroxy-6-methyl- PH including 1,3,3a, 7-tetrazaindene =
2.0 × 1.5% gelatin aqueous solution and 4 × per mol of silver
An aqueous sodium chloride solution containing 10 ⁻⁵ mol of K ₂ Ru (NO) Cl ₅ was applied by the double jet method at a potential of 95 mV for 3 minutes 30.
Half of the silver amount of the final particles was simultaneously added in a second to prepare 0.10 μm particles of the core. Then, silver nitrate aqueous solution and silver 1
An aqueous sodium chloride solution containing 4 × 10 ⁻⁵ mol of K ₂ Ru (NO) Cl ₅ per mol was added over 7 minutes in the same manner as described above to prepare silver chloride cubic particles having an average particle size of 0.13 μm (coefficient of variation). 13%). Then, after washing with water by a flocculation method well known in the art to remove soluble salts, gelatin was added, and compound-C as a preservative was added at 60 mg per mol of silver, pH 5.7, pAg = 7. .5
And 1 × 10 ^-5 mol of sodium thiosulfate per 1 mol of silver and 1 × 10 ^-5 mol of selenium sensitizer SE-.
Add 1 and 4 × 10 ^-5 mol of chloroauric acid and add 60 at 65 ° C.
After heating for a minute for chemical sensitization, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer was added at 1 × 10 ⁻³ mol per mol of silver (as final particles. , PH 5.7, pAg = 7.5, Ru = 4 × 1
It became 0 ^-5 mol / Ag mol.

[0221]

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<Preparation of Coating Solution for Emulsion Layer and Coating Thereof> The following compounds were added to the above emulsion, and the amount of coated gelatin was 0.9 g / m ² and the amount of coated silver was 2. on the following support including the undercoat layer. 7 g /
The silver halide emulsion layer was coated so as to have a size of m ² . 1-phenyl-5-mercapto-tetrazole 1 mg / m ² compound W 20 mg / m ² N-oleyl-N-methyl taurine sodium salt 10 mg / m ² compound-D 10 mg / m ² compound-E 10 mg / m ² compound-F 10 mg / m ² n-butyl acrylate / 2-acetoacetoxyethyl methacrylate / acrylic acid copolymer (89/8/3) 760 mg / m ² compound-G (hardener) 105 mg / m ² sodium polystyrene sulfonate 57 mg / m ² Further, the hydrazine-based nucleating agent of the present invention was added so as to be coated as shown in Table 3.

An emulsion protection lower layer and an upper layer were coated on the above emulsion layer. <Preparation of Emulsion Protecting Lower Layer Coating Liquid and Its Coating> The following compounds were added to a gelatin aqueous solution to give a gelatin coating amount of 0.6 g /
It was applied as a m ^2. Gelatin (Ca ⁺⁺ content 2700 ppm) 0.6 g / m ² p-sodium dodecylbenzene sulfonate 10 mg / m ² sodium polystyrene sulfonate 6 mg / m ² compound-C 1 mg / m ² compound-H 14 mg / m ² n- Butyl acrylate / 2-acetoacetoxyethyl methacrylate / acrylic acid copolymer (89/8/3) 250 mg / m ²

<Preparation of Emulsion Protecting Upper Layer Coating Solution and Its Coating>
The following compound was added to the aqueous gelatin solution, and the mixture was coated so that the coated amount of gelatin was 0.45 g / m ² . Gelatin (Ca ⁺⁺ content 2700ppm) 0.45g / m ² Amorphous silica matting agent 40mg / m ² (Average particle size 3.5μ, Pore diameter 25Å, Surface area 700m ² / g) Amorphous silica matting agent 10mg / m ² (average particle diameter 2.5 μ, pore diameter 170 Å, surface area 300 m ² / g) N-perfluorooctanesulfonyl-N-propylglycine potassium 5 mg / m ² p-sodium dodecylbenzenesulfonate 30 mg / m ² compound- C 1 mg / m ² Liquid paraffin 40 mg / m ² Solid disperse dye-G ₁ 30 mg / m ² Solid disperse dye-G ₂ 150 mg / m ² Sodium polystyrene sulfonate 4 mg / m ²

Then, a conductive layer and a back layer shown below were simultaneously coated on the opposite surface of the support. <Preparation of Coating Solution for Conductive Layer and Coating> The following compounds were added to a gelatin aqueous solution and coated so that the coating amount of gelatin was 0.06 g / m ² . SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 186 mg / m ² gelatin (Ca ⁺⁺ content 3000 ppm) 60 mg / m ² p-sodium dodecylbenzenesulfonate 13 mg / m ² dihexyl-α- Sulfosuccinate sodium 12 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Compound-C 1 mg / m ²

<Preparation of Back Layer Coating Liquid and Its Coating> The following compounds were added to a gelatin aqueous solution and coated so that the gelatin coating amount was 1.94 g / m ² . Gelatin (Ca ⁺⁺ content 30ppm) 1.94mg / m ² Polymethyl methacrylate fine particles (average particle size 3.4μ) 15mg / m ² Compound -i 140 mg / m ² Compound -J 140 mg / m ² Compound -K 30 mg / m ² compound-L 40 mg / m ² p-dodecylbenzenesulfonate sodium 7 mg / m ² dihexyl-α-sulfosuccinate sodium 29 mg / m ² compound-M 5 mg / m ² N-perfluorooctanesulfonyl-N-propylglycine Potassium 5 mg / m ² Sodium sulfate 150 mg / m ² Sodium acetate 40 mg / m ² Compound-E (hardener) 105 mg / m ²

(Support, Undercoat Layer) Biaxially stretched polyethylene terephthalate supports (thickness: 100 μm) were coated on both sides with the first and second undercoat layers having the following compositions. <Undercoat layer 1 layer> Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle size 3 μ) 0.05 g Compound-N 0.20 g Colloidal silica (Snowtex ZL: particle size 70 to 100 μm, manufactured by Nissan Kagaku Co., Ltd.) 0.12 g Water added 100 g Further, 10 wt% KOH was added to adjust the pH = 6, and the coating liquid was dried at 180 ° C. The dry film thickness was 0.
It was applied so as to be 9μ.

<Undercoat Layer Second Layer> Gelatin 1 g Methylcellulose 0.05 g Compound-O 0.02 g C ₁₂ H ₂₅ (CH ₂ CH ₂ O) ₁₀ H 0.03 g Compound-C 3.5 × 10 ⁻³ g Acetic acid 0.2 g Water was added 100 g This coating solution was coated at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness was 0.1 μm, to prepare a support including an undercoat layer. A sample was prepared as described above.

[0229]

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[0230]

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[0231]

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<Evaluation of Photographic Performance> (1) Exposure and Development Treatment The sample thus obtained was exposed by an optical wedge to a P-627FM printer manufactured by Dainippon Screen Co., Ltd., and automatically developed by Fuji Photo Film Co., Ltd. Machine FG-680AG and the developer of Example 1 were treated at 38 ° C. for 20 seconds, fixed, washed with water, and dried. The same fixing solution as in Example 1 was used. The development temperature and time were set to 38 for evaluation of running property unevenness.
The same procedure as in Example 1 was carried out except that the temperature was 20 ° C., and the results are shown in Table-3.

[0233]

[Table 3]

As is clear from Table 3, in the sample using the nucleating agent of Comparative Example, the gradation becomes soft and the sensitivity becomes NG level when running with a reduced replenishment amount,
With the sample using the nucleating agent of the present invention, even with low replenishment, the change in sensitivity and gradation was small, and favorable results were obtained. Also,
Even with the sample using the nucleating agent of the present invention, if the developing solutions A and D of the comparative example are used, development unevenness occurs or the photographic properties are greatly affected, but if the developing solutions B and C of the present invention are used, processing is performed. The unevenness and the effect on the photographic properties were small.

[0235]

The photosensitive material using the nucleating agent of the present invention and the developing solution containing the compound of the general formula (II) of the present invention give a pH of 1
It is a processing method of a silver halide black and white photographic light-sensitive material that can obtain stable photographic performance with little fluctuation in photographic properties and less unevenness even if the replenishing amount is reduced with a stable developing solution of less than 1.0. It was

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number for FI Technical indication G03C 5/305 G03C 5/305 5/31 5/31

Claims (3)

[Claims] 1. A support having at least one photosensitive silver halide emulsion layer, wherein an anionic group or a hydrogen atom of hydrazine is present in the vicinity of the hydrazine group in the emulsion layer or another hydrophilic colloid layer. A hydrazine nucleating agent having a nonionic group forming an intramolecular hydrogen bond, or at least one hydrazine nucleating agent and a nucleating accelerator selected from compounds represented by the following general formula (I): A silver halide photographic light-sensitive material characterized by containing
After exposure, (1) 0.2 to 0.75 mol / liter of dihydroxybenzene type developing agent, (2) 0.001 to 0.
06-mol / liter 1-phenyl-3-pyrazolidone-based or p-aminophenol-based auxiliary developing agent, (3)
0.3-1.2 mol / l of free sulfite ion,
(4) contains a compound represented by the following general formula (II), p
A method for developing a silver halide photographic light-sensitive material, which comprises processing with a developer having H of 9.0 to 11.0 and a replenishing amount of the developer of 225 ml / m ² or less. General formula (I) In the formula, R ₀ represents a difluoromethyl group or a monofluoromethyl group, and A ₀ represents an aromatic group. However, A ₀ is at least one non-diffusion group, a group promoting adsorption to silver halide, an alkylthio group, an arylthio group, a heterocyclic thio group, a quaternary ammonium group, and a nitrogen-containing hetero atom containing a quaternized nitrogen atom. It has a ring group, an alkoxy group containing an ethyleneoxy or propyleneoxy unit, a saturated heterocyclic group containing a sulfide bond or a disulfide bond, or a combination thereof as a substituent. General formula (II) In the formula, Y and Z are N or CR ₂ (R ₂ represents an alkyl group or an aryl group), R ₁ is —SO ₃ M, —COOM, —
_{OH, -NHSO 2 R 3, -SO} 2 NR 3 R 4 and -
An alkyl group, an aryl group or a heterocyclic group or an alkyl group substituted with at least one selected from the group consisting of NR ₅ CONR ₃ R ₄ ; Represent R ₃ , R ₄ and R ₅ represent a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms. M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium or a quaternary phosphonium. 2. The development processing method according to claim 1, wherein the developer is prepared by using a solid processing agent. 3. The nucleation accelerator is represented by general formula (III) or general formula (I
2. The silver halide photographic light-sensitive material according to claim 1, which is at least one compound selected from the group consisting of V) and compounds represented by general formula (V). General formula (III) General formula (IV): In the formula, A represents an organic group for completing the heterocycle.
B, and C is an alkylene, arylene, _{alkenylene, -SO 2 -, - SO -} , - O -, - S -, - N
(R ₅ )-represents one or a combination thereof. However, R ₅ represents an alkyl group, an aryl group, or a hydrogen atom. R ₁ and R ₂ each represent an alkyl group, and R ₃ and
Each R ₄ represents a substituent. X represents an anionic group, but X is not necessary in the case of an internal salt. General formula (V) In the formula, R ₁ , R ₂ and R ₃ are an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group,
Represents a heterocycle residue. m represents an integer, L represents an m-valent organic group bonded to a P atom and its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X represents L.
May be connected.